Purified Silicon, Devices and Systems for Producing Same

ABSTRACT

The present disclosure provides devices and systems that utilize concurrent and countercurrent exchange platforms to produce purified silicon.

BACKGROUND

The present disclosure is directed to devices and systems for producingpurified silicon, and the resultant purified silicon.

Extreme purity in semiconductor silicon is necessary, and best availablesilicon purity is prized in semiconductor production. Improved siliconpurity translates into improved semiconductor production statistics andimproved semiconductor operation. Silicon based photocell efficiency andphotocell production could also be more efficient if much purer siliconwas available cost effectively for silicon based photocell production.In general, given ideal processing, the ideal silicon for any photocellor semiconductor purpose (setting cost aside) would be purity so highthat no elements other than silicon were detectable in the silicon,purity so high that the exact value of the concentrations of impuritieswere immaterial for any practical purpose, and in the ideal limit,perfect or asymptotic purity, where the presence of single atoms ofimpurity elements in the silicon was improbable. Such “perfect for allpractical purposes” purity would provide maximum control ofcrystallization, P—N doping, resistivity, and charge carrier lifetime.Every impurity element in the Periodic Table slows, degrades anddisorders silicon crystallization to some degree. Elements in electronacceptor group 13 (B, Al, Ga, etc) and electron donor group 15 (N, P,As, Sb etc) determine whether the dominant charge carrier in the siliconis electrons or holes, and are very important for resistivity. Thetransition metals all reduce charge carrier lifetimes, with thedeleterious effect on charge carrier lifetime increasing moving to theleft and down on the periodic table. Ta, Mo, Mb, Zr, W, Ti, and V atomssignificantly reduce crystalline silicon charge carrier lifetimes at subpart per billion concentrations. For the best possible photocells, orthe best semiconductors (especially for high frequency operation, orwhere energy costs are important, as in cell phones and tablets) onewants the longest available charge carrier life and the highestavailable silicon resistivity.

The energy costs of silicon production are also important. Energy costsare especially important for silicon photocell production if siliconphotocells are to have a practical chance of replacing fossil fuelenergy production on a world scale. Current photocell energy production(which is mostly from silicon based photocells) is less than 1% of worldenergy consumption. At that relatively small scale, the energy cost ofrefining the silicon may not be crucial. However, if energy productionfrom silicon photocells is ever to approach world energy consumption, soas to significantly displace fossil fuel production, it would bedesirable to greatly reduce the energy cost of refined siliconproduction—and desirable to do so with much higher purities than areavailable in “solar grade silicon” now.

It is estimated that the energy cost to manufacture 1 kg of siliconwafers for photocells now is about 1000 kilowatt hours. Energy paybackfor current production silicon photocells is therefore more than twoyears. Very rapid growth of multi-terawatt scale silicon photocelldeployments needed to significantly replace world fossil fuels use withthis silicon energy cost would require inconvenient and probablycommercially impossible energy inputs. The scale of silicon productionneeded to produce multi-terawatt outputs of silicon based photocells islarge. Assuming that 500 watts of photocells can be made per kilogram ofpurified silicon, production of 10¹² watts of photocells in ten years ofcontinuous production would take production of about 550 tons ofpurified silicon per day during that decade of production. To replaceworld consumption of fossil fuels with photocells, something aroundfifty times this production would be needed—or something around 13,750tons/day of purified silicon every day for twenty years. For thisproduction to be feasible in terms of energy paybacks, it would bedesirable to cut current art silicon purification energy costs by afactor of ten or much more.

Looking at thermodynamic limits, the theoretical energy requirement ofsilicon purification and wafer fabrication is something less than twicethe energy requirement to melt the silicon—something less than 1.5kilowatt hour per kilogram of silicon, or less than 1% of current energycosts. But the actual history of incremental development has notinvolved any substantial, sustained effort to converge on these lowenergy costs, which would involve committing to technology fundamentallydifferent from established patterns. Historical efforts to produce“solar grade silicon” have involved variations on a theme withinherently high energy costs. Proceeding according to this theme,silicon is oxidized to a volatile (SiCl₄; SiHCl₃; SiI₄; SiH₄, SiHCl₃;Si_(n)F_(2n+2); SiHBr₃; or SiF₄) and that volatile is multiplydistilled. The purified volatile is then reduced to solid silicon in areactor. All of these approaches involve energy costs far higher thanthe thermodynamic limit. The basic silicon volatile distillation andreduction pattern locks in energy costs and capital costs that do notconstrain current relatively small scale photocell deployments, but theenergy costs of this established pattern rule out the enormousproduction scales necessary for photocells as a full solution to theworld's energy scarcity and global warming problems, where production oftens of terawatts of photocells will be necessary, and will have to beproduced within a relatively few years.

If photocells are to practically replace fossil fuels, one of thetechnical requirements will be a process for purifying silicon with muchlower (ideally arguably minimum possible) energy costs, much lower(arguably minimum possible) operating costs, and the capacity for highproduction rates (up to millions of kg/day). The highest possiblesilicon purity would be desirable for this process, ideally purity muchhigher than any available today, to facilitate the maximization ofsilicon photocell efficiency and to facilitate the minimization ofsilicon photocell production cost.

Setting the issue of photocell production aside, there is also asignificant and ongoing market need to improve the purity-cost tradeofffor semiconductor silicon, and for silicon supplied for metal castingand silicone feedstock production purposes as well.

SUMMARY

The present disclosure provides devices and systems that utilizeconcurrent and countercurrent exchange platforms to produce purifiedsilicon.

The present disclosure produces a device for purifying silicon. In anembodiment, the device includes a vessel having a top end, an opposingbottom end, and a sidewall extending between the opposing ends anddefining a chamber. A silicon inlet is present at a top portion of thevessel for introducing molten silicon into the chamber. A gas injectionstructure is present at a bottom portion of the vessel. The gasinjection structure has a plurality of orifices for introducing a gascomprising oxygen into the chamber. The introduction of the gas producesa plurality of in situ silica-walled oxygen beads in the chamber. Thedevice includes a countercurrent exchange section located between thesilicon inlet and the gas injection structure. The countercurrentexchange section includes (1) a controlled downward flow of the moltensilicon and (2) a controlled upward flow of the beads. Thecountercurrent flow between the molten silicon and the silica-walledoxygen beads enables impurities present in the molten silicon totransfer into silica walled oxygen beads to form purified moltensilicon.

The present disclosure provides another device. In an embodiment, adevice for purifying silicon is provided and includes a vessel having atop end, an opposing bottom end, and a plurality of concentric columns.The columns are in fluid communication with each other. The deviceincludes a central column having a silicon inlet at a top portion of afirst column for introducing molten silicon into a bed of a plurality ofsilica particles to form a slurry. The device includes a first channelin fluid communication with a bottom portion of the central column forreceiving a portion of the slurry. The slurry upwardly flows in thefirst channel. The device includes a second channel in fluidcommunication with the first channel for receiving a portion of theslurry. The slurry downwardly flows in the second channel.

The present disclosure provides another device. In an embodiment, adevice for purifying silicon is provided and includes a vessel having atop end, an opposing bottom end, and a sidewall extending between theopposing ends. The sidewall defines a chamber. The device includes asilicon inlet at a top portion of the vessel for introducing siliconparticles into the chamber. The silicon particles have a temperaturegreater than 1350° C. The device includes an injection structure at abottom portion of the vessel. The injection structure has at least oneorifice for introducing a molten salt composition into the chamber. Themolten salt composition has a temperature greater than 1350° C. Themolten salt includes an oxidizer dissolved in the molten salt. Thedevice includes a countercurrent exchange section located between thesilicon inlet and the injection structure. The countercurrent exchangesection includes (1) a controlled downward flow of the siliconparticles, and (2) a controlled upward flow of the molten saltcomposition. The countercurrent flow between the silicon particles andthe molten salt composition produces purified silicon particles.

An advantage of the present disclosure is a silicon production systemthat produces purified silicon at minimal economic cost and/or minimalenergy cost.

An advantage of the present disclosure is the production of purifiedsilicon utilizing concurrent and countercurrent selective oxidationsolvent exchanges using flow structures similar to exchanges used inpacked bed and expanded bed column chromatography.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1a, 1b, 1c, 1d, and 1e show flow relations with respect to Darcyflow important to understanding the current disclosure. Chromatographyinvolves Darcy flows where the eluent passage length and the transittime for any particular chemical is very uniform. The impurity sorptionand complexing necessary for silicon purification involves similarflows, with multiple equilibria closely similar to “heights equivalentto a theoretical plate”, but the flow paths can be curved and transittimes for different streamlines can vary so long as every streamlineinvolves a large enough number of effective equilibrations.

FIGS. 2a, 2b, and 2c illustrate concurrent and countercurrentsilicon-solvent flow using a theoretical plate model, and illustratethat the notion of countercurrent and concurrent exchange makes sensefor curved streamlines.

FIG. 3 illustrates the arithmetic of countercurrent purification for aplate model, showing the high purification factors possible with wellordered countercurrent Darcy flows.

FIG. 4 illustrates the basic low energy purification scheme of thecurrent disclosure, where silicon and solvent are heated above themelting point of silicon, and concurrently and countercurrentlycontacted above the melting point of silicon so that the impuritiestransfer to the solvent. The purified silicon is then solidified andcooled, and the impurity-laden slag is disposed of.

FIG. 5 shows a device for purifying silicon in accordance with anembodiment of the present disclosure. The FIG. 5 device streamlines arenearly as well organized as the flows in column chromatography. A sourceof partly purified molten silicon feeds a countercurrent expanded bedsilicon purifier where silicon flows down through an upwardly movingpacked or expanded bed of thin walled silica spheres formed in place bybubbling oxygen into the silicon.

FIG. 5A is a sectional view of the device of FIG. 5 taken along line A-Aof FIG. 5.

FIG. 5B is a sectional view of the device of FIG. 5 taken along line B-Bof FIG. 5.

FIG. 6 shows a top plan view of the device of FIG. 5. FIG. 6 shows theplacement of molten silicon inputs, a gas pressure and volume supply forestablishing the gas-liquid interface of the interstitial volume betweenthe particles and for softening the particles, for example with steam,and suction points breaking and removing the silica and impurities.

FIG. 7 is a schematic representation of a thin walled spherical silicaparticle (or bead) formed by bubbling oxygen into the molten silicon ofthe device of FIG. 5.

FIG. 8 shows a “coarse” purifier in accordance with an embodiment of thepresent disclosure. In FIG. 8, silica and silicon are mixed and contactconcurrently in a buoyancy stabilized Darcy flow. The impurities in thesilicon are transferred to the silica during this intimate and prolongedconcurrent contact. The silica forms a glassy slag. The glassy slag andthe molten silicon are then separated by differential density.

FIG. 8A is a sectional view taken along line A-A of FIG. 8.

FIG. 9 is a sectional view of a countercurrent exchanger in accordancewith an embodiment of the present disclosure. In FIG. 9, silicaintroduced as a slurry and removed as a slurry flows countercurrentlywith molten silicon to produce a large number of theoreticalcountercurrent exchanges between the silicon and the silica.

FIG. 9A is a sectional view taken along A-A of FIG. 9.

FIG. 10 is a sectional view of a device for purifying silicon inaccordance with an embodiment of the present disclosure. In FIG. 10, aconcurrent exchanger similar to the coarse exchanger of FIG. 8 and acountercurrent exchanger similar to FIG. 9 are connected in series in acombined structural form.

FIG. 10A is a sectional view taken along line A-A of FIG. 10.

FIG. 11 is a schematic representation of a device for purifying siliconin accordance with an embodiment of the present disclosure. In FIG. 11,a Darcy flow buoyancy stabilized countercurrent exchange for siliconpurification is shown. In FIG. 11, a selectively oxidizing molten saltselectively oxidizes and removes the elements in silicon that formsilicides below the melting point of silicon, and also selectivelyoxidizes and removes from surfaces the elements that diffuse in thesilicon crystals rapidly enough to diffuse to surfaces.

FIG. 12 is a schematic representation of a liquid-liquid countercurrentexchange through a packed sapphire bead column with molten silicon asthe sapphire nonwetting liquid and a molten salt as the sapphire wettingliquid. The molten salt is a mixture of NaCl, Na₂S, Al₂S₃ or other saltsincluding enough excess sulfur for a significant partial pressure ofsulfur, pS, and enough silicon sulfide partial pressure to inhibit anynet silicon oxidation. The high pS molten salt selectively oxidizes anddissolves noble metals from the silicon in an isothermal many HETPexchange. The molten salt is recirculated through electrolytic platesthat remove the noble metals from the molten salt so that therecirculated clean solvent supplied to the countercurrent exchange isextremely pure with respect to the noble metals.

FIG. 13 is a schematic representation of an argon bubbling arrangementwith argon recirculation for removing oxygen that is not removed by theselective oxidation purification stages. This deoxidation stage is alast purification stage prior to solidification.

FIGS. 14 to 20 are a series of schematic diagrams of purifier componentsarranged in series for effective purification, each carrying out thebasic low energy silicon purification scheme of the present disclosure.

FIG. 14 is a schematic flowchart showing an ultrapurifier arrangement, amelter of relatively pure silicon input, the thin walled silica sphereultrapurifier, followed by argon deoxidation.

FIG. 15 is a schematic flowchart showing a melter feeding molten siliconto a coarse purifier which feeds molten silicon to a thin walled silicasphere ultrapurifier, followed by argon deoxidation.

FIG. 16 is a schematic flowchart showing a melter feeding molten siliconto a coarse purifier which feeds molten silicon to a countercurrentexchanger similar to that of FIG. 9 which feeds a thin walled sphereultrapurifier, followed by argon deoxidation.

FIG. 17 is a schematic flowchart showing a melter feeding molten siliconto a coarse purifier which feeds two countercurrent exchangers similarto that of FIG. 9 arranged in series, followed by argon deoxidation.

FIG. 18 is a schematic flowchart showing a melter feeding molten siliconto a coarse purifier followed by a countercurrent molten salt exchangepurification stage feeding silicon to a thin walled silica sphereultrapurifier, followed by deoxidation.

FIG. 19 is a schematic flowchart showing a solid ground silicon purifierfollowed by a melter which then feeds the molten silicon to a thinwalled silica sphere ultrapurifier, followed by deoxidation.

FIG. 20 is a schematic flowchart showing a solid ground silicon purifierfollowed by a melter which then feeds the molten silicon to acountercurrent exchanger similar to that of FIG. 9, followed bydeoxidation.

Definitions

Any reference to the Periodic Table of Elements is that as published byCRC Press, Inc., 1990-1991. Reference to a group of elements in thistable is by the new notation for numbering groups.

Unless stated to the contrary, implicit from the context, or customaryin the art, all parts and percents are based on weight and all testmethods are current as of the filing date of this disclosure.

For purposes of United States patent practice, the contents of anyreferenced patent, patent application or publication are incorporated byreference in their entirety (or its equivalent US version is soincorporated by reference) especially with respect to the disclosure ofdefinitions (to the extent not inconsistent with any definitionsspecifically provided in this disclosure) and general knowledge in theart.

The numerical ranges disclosed herein include all values from, andincluding, the lower and upper value. For ranges containing explicitvalues (e.g., 1 or 2; or 3 to 5; or 6; or 7), any subrange between anytwo explicit values is included (e.g., 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5to 6; etc.).

“Composition” and like terms refer to a mixture or blend of two or morecomponents.

The terms “comprising,” “including,” “having,” and their derivatives,are not intended to exclude the presence of any additional component,step or procedure, whether or not the same is specifically disclosed. Inorder to avoid any doubt, all compositions claimed through use of theterm “comprising” may include any additional additive, adjuvant, orcompound, whether polymeric or otherwise, unless stated to the contrary.In contrast, the term, “consisting essentially of” excludes from thescope of any succeeding recitation any other component, step, orprocedure, excepting those that are not essential to operability. Theterm “consisting of” excludes any component, step, or procedure notspecifically delineated or listed. The term “or,” unless statedotherwise, refers to the listed members individually as well as in anycombination. Use of the singular includes use of the plural and viceversa.

An “impurity” in silicon is any element in the periodic table except forsilicon. There are 98 natural elements, and in current practice it isreasonable (based on general knowledge, sometimes on analyticalinformation from a vendor, and occasionally on measurement) to assumethat any substantial volume of silicon, metallurgical or purified, hassome concentration of (some numerically large number of) atoms of all ornearly all of these natural elements.

An impurity concentration in silicon is the molar or weight fraction ofthis impurity element in a mass of silicon, and for chemicalcalculations the molar values are more convenient, and used in thisparagraph. There are 6.02×10²³ atoms of silicon per mole, so aconcentration of the impurities (Na, Ca, Fe, Al, etc) of 1 part perbillion would be 6.02×10¹⁵ atoms (of Na, Ca, Fe, Al, etc) in a mole ofsilicon—a low concentration but still a large number of atomspractically uncountable with real instrumentation. Concentrations ofimpurity atoms in silicon are measured (in the bulk silicon and atsurfaces) by various spectroscopic means, including nondestructive meansthat measure at surfaces and mass spectroscopy that involves destructionof the silicon sample. The art of silicon impurity measurement is anextensive and advancing art. Detection limits and resolution are subjectto continuous improvement because silicon purity is commerciallyimportant. Detection limits are generally well below the part perbillion level for all the elements in the periodic table and in specialcases can be as low as a part per trillion (6.02×10¹² atoms/mole), stillan enormous number of atoms of impurity per mole of silicon. In a verysensitive mass spectroscope ionized stream, individual atoms ofidentified elements can sometimes be detected one by one, but the numberof atoms that can be sampled in this way is small. With field ionmicroscopy atoms can also be seen one by one, but again, the number ofatoms that can be sampled is small.

One can infer concentrations below detection limits (concentrations thathave not been and cannot be measured) reasoning from processes thatoccur with detectable concentrations and that are understood to occur anatom or molecule at a time, and assuming that these processes continuein the same way according to the same chemical and physical logic whenthe concentration of an impurity falls below detectable limits. Forinstance, if a countercurrent purification process working with a sourceof perfectly pure solvent is understood to occur in a sequence ofsimilar stages, with each stage reducing the concentration of animpurity element j by a factor of m_(j) then the total purificationfactor after N stages is m_(j) ^(N). This arithmetic applies toconcentrations that can be measured, and this same arithmetic can beinferred to go on by a logic of extrapolation. The inference followsthat the process continues to act in the same way for larger values of Nso that it produces purification factors that correspond toconcentrations of impurity element j that may be below or far belowdetectable concentrations. An ideal silicon purifier would in factreduce all the impurity elements to concentrations far below detectableconcentrations in a way that was both practical and fully understood,based on fully understood inferences validated in every way thatmattered for practical function. Inferences of lower than measurableconcentrations must be based on questionable but often useful logic ofmodel-system correspondence. The validity of such inferences aboutconcentration can be judged by both scientific and engineering logic,including the logic of systems in more-or-less close analogy to thesystem in question that have been measured or can be measured. Theinferences about concentrations can also be checked by measurements onthe system involved that are in fact possible and are in fact done. Ifinferences from a model indicate that an impurity concentration shouldbe well below the threshold of delectability and that impurity isdetected, there is something wrong with the assumptions of the modelapplied to the case in question that may offer guidance introubleshooting either the model or the apparatus under test.

Molten silicon is elemental silicon in liquid phase, more or less pureor impure. The melting point of pure silicon is 1414° C. Molten siliconhas a viscosity and kinematic viscosity roughly similar to those ofwater at room temperature, so that flow analogies between aqueous flowsat room temperature and flows involving molten silicon at temperaturesabove 1400 C for the same geometries and the same pressure gradients canbe close.

Silica is the chemical SiO₂ in any form and in any purity that ispredominantly SiO₂, whether that be sand or a specialized and treatedsand such fracking sand, or SiO₂ formed by oxidation of silicon, formedby refinement from sodium silicate, or formed by some other chemicalprocess.

A silicate is a composition of SiO₂ and other elements. The most commonform of silicate is glass. Except for the inert gases, every element inthe periodic table can chemically bond with and/or significantlydissolve in silicate glasses. Equilibrium conditions often stronglyfavor incorporation of an oxidized impurity into a glass, but theprocess is limited by diffusion. Diffusivities in glassy melts aregenerally low, and diffusion rates in glasses and glassy slags can beenormously slow compared to many liquids such as water. The viscosityand diffusivity of glasses are closely related and roughly proportional,and both glass viscosity and glass diffusivity are strongly dependent ontemperature and composition. Many useful glass compositions are widelyused, glasses are widely studied, and glass and glassy silicate slagsare used to immobilize and dispose of radioactive waste material thatincludes every natural element.

Selective oxidation solvent purification of silicon is the processwhereby impurity elements in solid or liquid silicon (dissolved insilicon in a chemically reduced form) come into atomic or molecularscale contact with a solvent immiscible in the silicon which oxidizesthese impurities without oxidizing the silicon, where the solvent thencomplexes with or otherwise dissolves the oxidized impurities, carryingthese oxidized impurities away from the silicon and therefore purifyingthe silicon.

Selective oxidation solvents for liquid silicon selective oxidationpurification: silica and glassy silicates. Silica and glassy silicatesare effective selective oxidizing solvents for molten silicon, servingas both the oxygen source for the selective oxidation and as aneffective solvent for the impurities in the molten silicon. Silica andglassy silicates would be nearly ideal for selective oxidizing solventsfor silicon except for the extremely low diffusivities that moltensilica and molten glasses have, which dictate substantial silicon-silicacontact areas, short diffusion distances, extended contact times, andordered flows for complete and well-ordered mixing. Silica and glassysilicates are immiscible in molten silicon. The silicon-silica contactgenerates enough oxygen (an equilibrium oxygen concentration x_(o) of5.7×10⁻⁵ and a partial pressure, pO₂, of roughly 5×10⁻⁵ atmospheres) tooxidize essentially all the impurities in the molten silicon withoutoxidizing the silicon itself. Research work largely motivated towardsradioactive waste disposal has generated electrolytically measuredvalues of the Gibbs free energy of most elements in pure silica and insilica glasses over a wide range of pO₂s, and the Gibbs free energy ofmost elements in molten silicon is also known. Equilibria can becalculated for concentration ratios of impurities between silicon andsilica. At the relatively high partial pressures of oxygen in thesilicon and silica glass in contact with molten silicon, equilibriafavor the silica solvent by enormous factors, with the (oxidized)impurities typically more soluble in the silica or glass than thesilicon by factors of millions, billions or much more. Equilibriastrongly favoring the glass versus the silicon apply to almost all theelements in the Periodic Table, with the partial exception of copper andthe platinum group metals, which are soluble in glasses containingsulfates.

Thermodynamics and phase stability in the Si—O system by S. M. Schnurre,J. Grobner, and R. Schmid-Fetzer (Journal of Non-Crystalline Solids, 336(2004) 1-25) sets out the basic relations that make the silica-siliconcontact an effective oxygen source for selective oxidation ofimpurities, especially in discussions with respect to Schnurre FIGS. 10,16, and 17. Schnurre FIG. 10 plots the Gibbs Free energy of amorphoussolid silicon monoxide, SiO, compared to a mixture of silicon and SiO₂with the same silicon/oxygen ratio over a range of temperaturesincluding both solid and liquid silicon. An important fact is thatamorphous solid SiO is unstable at all temperatures—the stable forms thesilicon and oxygen combine into are molten silicon and SiO₂. Liquid Siand crystalline or glassy SiO₂ (which are thermodynamically quite close)are different phases, and can be usefully considered as phases inanalogy with the solid and liquid phases of H₂O. At the melting point ofsilicon, a mixture of Si and SiO₂ with a gas phase interface will be inequilibrium with 11.4×10⁻³ bar of gaseous SiO (this value may be subjectto experimental error, and may change a few percent, but it is taken asa fixed value to emphasize that the phase transition in the Si—O systemis as sharp as the water-ice transition in water at O degrees C.). At2300K (610° C. above the melting point of silicon) SiO at the muchhigher pressure of one bar is at equilibrium with molten silicon andSiO₂. Schnurre FIG. 16 plots the Si—O phase diagram showing the gasphase equilibria at 1 bar pressure over a range of temperatures, withx_(o), the mole fraction of oxygen in the silicon-oxygen system mixture,on the horizontal axis, with x_(o) ranging from 0 to 1. Schnurre FIG. 17plots the portion of that Si—O system phase diagram at the extreme left,with the full horizontal scale ranging from x_(o)=0 to x_(o)=7×10⁻⁴, andshows a point at x_(o)=0.57×10⁻⁴ where Si, SiO₂, and gaseous SiO at0.0114 bar coexist.

The value of x₀=0.57×10⁻⁴ at 1414 C for the silicon oxygen system can bethought of as a direct analogy to temperature in the water-ice system atO C in the presence of saturated vapor. If the temperature goes above OCin the water-ice system at standard pressure there is no ice phase. Thetemperature in a well equilibrated water-ice system cannot fall below 0C until all the water has turned to ice. The temperature in theequilibrated water-ice system cannot go above 0 C until all the ice hasmelted. The relations of x_(o) at a submerged silicon-silica contact areanalogous. If x_(o) in the liquid silicon is less than 0.57×10⁻⁴ in thepresence of SiO₂, the SiO₂ can be thought to melt away—the silicon andoxygen in the SiO₂ are both dissolved into the liquid silicon, and thisdissolution continues until an x₀=0.57×10⁻⁴ oxygen concentration isestablished in the liquid silicon or until the SiO₂ phase disappears.For equilibrium going in the other direction, if x_(o) in the liquidsilicon somehow exceeds 0.57×10⁻⁴ (a supersaturated condition) anyoxygen in excess of 0.57×10⁻⁴ will transfer (along with a correspondingamount of silicon) to the SiO₂ phase.

Darcy flows, where molten silicon flows through silica particles, can beconsidered as “x_(o) fixing baths” for molten silicon, in analogy totemperature fixing ice baths. The x_(o) for such a bath, using puresilicon and pure silica, can be computed directly from the measurementsshown in FIG. 2 and FIG. 3 of Oxygen Solubility in Silicon Melt Measuredin Situ by an Electrochemical Solid Ionic Sensor by A. Seidl and G.Muller. x_(o) is fixed at any set temperature, and increases withtemperature according to an Arrhenius relation as temperature increasesabove the melting point of silicon. The partial pressure of oxygen (inthe molten silicon and silica glass contact at 1420 C) corresponding tox₀=0.57×10⁻⁴ is a pO₂ that can be computed from the relations of Seidland Muller. The computed pO₂ is roughly 5×10⁻⁵ atmospheres.

Glass is used to immobilize nuclear wastes, and the pO₂ values in whichdifferent ions of elements dissolve in glasses has been a subject ofintense and long-running research, and so the effectiveness of silicaand glasses as silicon purification solvents can be reliably calculatedworking through the process by which the Gibbs free energy of animpurity changes as it diffuses from molten silicon into silica at setvalues of pO₂. A graph plotting the percentage of redox couples in areduced state for many elements versus pO₂ is shown as FIG. 1 in RedoxChemistry in Candidate Glasses for Nuclear Waste Immobilization by HenryD. Schreiber and Angels L. Hockman, J. Am. Ceram. Soc., 70(8) 592-94(1987). A pO₂ of 5×10⁻⁵ atmospheres is well within the processing rangefor immobilizing impurity elements in glasses. The activities and Gibbsenergies of most elements in molten silicon have been measured, and theGibbs free energies of essentially all the elements have been measuredin glass, with many results set out in “A comprehensive electromotiveforce series of redox couples in soda-lime silicate glass” by Henry D.Schreiber, Nicholas R. Wilk, Jr., and Charlotte W. Schreiber, Journal ofNon-Crystalline Solids 253 (1999) 68-75. At a pO₂ of 5.×10⁻⁵atmospheres, equilibrium favors the glass by large factors for mostelements. For iron, the glass is favored by a factor of 2.8×10¹¹; fornickel, the glass is favored by a factor of 3.5×10⁸. For most othertransition elements, and all the group 1 and group 2 elements, thefactors favoring the glass are higher.

DETAILED DESCRIPTION

The present disclosure provides silicon purification by a series ofconcurrent and countercurrent selective oxidation solvent exchangesabove 1414° C. Some embodiments utilize Darcy flow structures similar tothose used in packed bed and expanded bed column chromatography. Oncethe total silicon impurity concentration is low enough, completepurification for most or all impurity elements can be accomplished withan orderly expanded bed countercurrent purifier using thin walled silicaspheres formed-in-place by oxygen bubbling as the solvent particles,followed by argon bubbling to remove dissolved oxygen (and perhapsdissolved sulfur) from the molten silicon. Earlier stages of siliconpurification can be accomplished in many ways. Flowing the moltensilicon through a packed bed or expanded bed of silica particleseffectively removes most impurity mass. Selective oxidation of silicidesand rapidly diffusing impurity elements through a packed or expanded bedof ground silicon between 1350° C. and 1414° C. can also be an effectivepurification step.

Applicant surprisingly discovered that silica can function both as anoxidizing solvent and as an oxygen source/solvent in the purification ofsilicon. It also seems likely that most practitioners today will besurprised that mixing limitations with silica or glassy solvents presson design decisions as severely as they do. To many experiencedmetallurgists and material scientists it will seem unthinkable that SiOis compatible with any relatively high pO₂ such as 5×10⁻⁵ atmosphere.Addition of silicon into molten aluminum, iron, or other metals servesas an oxygen getter, and this getter function is the main use forsilicon on a mass basis. SiO is silicon with half the oxygen of thefully oxidized form, SiO₂, and also acts as an oxygen getter except whenit is dissolved in molten silicon. In an Ellingham diagram, the 2SiO+O₂=2 SiO₂ line at 1414 C is about 5×10⁻¹⁷ atmospheres—extremelyreducing. In a similar way, silicon monoxide gas that condenses onsilica or a silica glass surface strongly lowers the pO₂ of the glass.The addition of silicon and oxygen in a 1:1 ratio decreases the ratio ofoxygen to silicon in the silica, which is 2:1, gettering any dissolvedoxygen in the silica.

Sorption of a SiO molecule into molten silicon is qualitativelydifferent from sorption of SiO onto any other surface. The additionalsilicon atom incorporates into the covalently bonded, flawedmacromolecule that is the liquid silicon, and does not change itschemical character, even infinitesimally. The oxygen atom in the SiOincreases the concentration of oxygen in the silicon, x_(o), increasingthe pO₂ of the silicon. A body of silica, immersed in molten silicon atan oxygen concentration x_(o), but not in direct contact with gas phaseSiO, will gain an oxygen fugacity pO₂ equal to the pO₂ of the moltensilicon in which it is immersed.

Complications as silica solvent takes up impurities and becomes silicaglass solvent. As silica solvent immersed in molten silicon complexeswith the oxides of impurities that form on the glass-silicon interfacesurface, the silica glass becomes less viscous, diffusivities in theglass increase, and the percentage of silicon oxides compared to otheroxides in the glass formed from the silica decreases—which means thatsome silicon atoms from SiO₂ transfer to the liquid silicon, freeing upoxygen atoms to form metal oxides (Al₂O₃, MgO, CaO, FeO and FeO₂, NiOand others) which dissolve into the glass. Some of these substitutionreactions simply follow from the fact that the metals involved havehigher free energies of oxide formation on an energy/mole basis thansilicon. Metals with these higher energies of formation (including Ca,Mg, Al) typically make up roughly half of the mass of the impurities inmetallurgical silicon. Substitution reactions involving these metalswill occur with any silica containing slag, regardless of whether thatslag is a glass or a much less viscous and much less glass-like liquid.These substitution reactions will occur regardless of pO₂ in the siliconand the slag.

The reactions 2 Al+3 SiO₂→3 Si+2 Al2O₃; 2 Ca+SiO₂→Si+2 CaO; 2Mg+SiO₂→Si+2 MgO; and many more simply depend on a stronger metal-oxygenbond displacing a weaker silicon-oxygen bond.

However, substitution reactions for the ionized (oxidized) form of manyother metals such as Cd, Zn Co, Fe, Se, Sn, Ni, Ti, V, Cr, Cu involvereactions, including these for iron and nickel (2 Fe+SiO₂→Si+2 FeO(complexed in glass); 2 Ni+SiO₂→Si+2 NiO (complexed in glass)) that onlyoccur with an extremely viscous glassy slag, and that depend on the highGibbs energy of solution of these element ions in the glass. This energyof solution in silica and other glasses has been measured, for instancein Schreiber, Wilk, and Schreiber, op cit. and has been used extensivelyin radioactive waste disposal.

Silica solvent in contact with molten silicon has a complicated andpotentially useful relation with sulfates. Sulfate ion solubility inglasses is generally less than 0.6%. If the concentration of sulfate ionis above this solubility limit, sulfate salts form that have lowviscosities comparable to water. These sulfate salts are immiscible withboth the glass and the molten silicon. Sulfates in both the glass andthe salt form can be useful for dissolving metals such as gold, silver,and the platinum metals at a lower pO₂ than would otherwise benecessary. Sulfates adsorbed on glassy surfaces can inhibit fusion ofdifferent glassy particles suspended in molten silicon that contact eachother. It may therefore be useful to add Na₂SO₄ or CaSO₄ to the silicasolvent.

In coarse purification, there are reasons to economize on the mass ofsilica used per mass flow of silicon, both because the silica costssomething (fracking sand now costs roughly 5 cents/kg) and because ittakes energy to heat the silica up to the melting point of silicon.There are also advantages to lowering slag viscosity, which complexingwith impurities does, and which can also be done by adding additivessuch as Na₂O or H₂O which soften the glass, because it allows impurityions to diffuse more rapidly from particle surfaces to the center of theparticles. In ultrapurification, where the silica is oxidized directlyfrom purified silicon that could otherwise be sold or used, there isalso reason to economize on silica. In both cases there are alsoadvantages in using ample silica. The closer the glass solvent is topure silica, the easier it is to understand and calculate the solvent.

Selective oxidation solvents for liquid silicon selective oxidationpurification: selectively oxidizing molten salts. Some impurityelements, particularly gold, silver and the platinum series metals,oxidize more easily with sulfur than with oxygen. A molten salt (forexample a mixture of NaCl, KCl, Na₂S and other salts) with a high enoughpartial pressure of sulfur and an equilibrium concentration of siliconsulfides can selectively oxidize and dissolve these impurities withoutnet oxidation of the liquid silicon. Molten salts have the advantagethat they have much lower viscosities and much higher diffusivities thanglasses. Noble metals dissolved in molten salts can be reclaimed byelectrolysis, purifying the molten salt for recirculation.

Selective oxidation solvents for solid silicon. Solid silicon has anextremely high oxidation resistance. This oxidation resistance remainshigh at temperatures close to its melting point (1350-1400° C.), atemperature where many impurity elements have a relatively highdiffusivity in the silicon crystal, and a temperature where manyimpurity elements that react to form silicides form liquid silicides.Molten salts with a high partial pressure of sulfur can oxidize theseliquid silicides, and can oxidize impurities that have diffused to theexposed surfaces of silicon crystals, with essentially no oxidation ofthe crystalline silicon. The molten salt solvent then complexes with orotherwise dissolves the oxidized impurities, carrying these oxidizedimpurities away from the solid silicon and therefore purifying thatsolid silicon. Impurities that form molten silicides and impurities thathave high solid diffusivities in the silicon can be purified in thisway. However, selective oxidation purification of solid silicon isineffective for low solid diffusivity elements close to silicon on theperiodic table, including B, Al, P, and As, because diffusion of theseelements in the silicon crystal is so slow that their rate of diffusionto solid silicon surfaces is negligible.

Correspondence between model systems and practical systems in the caseof the present disclosure, where some analogies to column chromatographypractice are close: Inferences about system purification based onmore-or-less complete analogies to column chromatography, and inferencesbased on chemical and physical calculations based on more-or-lesstrusted principles, can produce calculated results and calculatedconcentrations based on models that can sometimes be compared to directmeasurements. The models involve mechanical, chemical, and mathematicalarguments and descriptions, with equations in particular forms.Variables that can be estimated and plugged into equations yieldpredictions with numerical values applicable to more-or-less clearlydefined contexts. The mathematical form of the models applied to apractical process may not be (and in most cases probably cannot be)exactly correct, and the estimated values of variables, based in turn onfallible measurements, fallible models, and fallible assumptions, maynot be (and probably are not) exactly right. Experience shows thatmodels in engineering and science are indispensable for work butexperience also shows that they are often misapplied, and often inexact.Experience also shows that some models, applied within limits welltested by experience and measurement, can be reliable enough for wellspecified practical purposes, and can sometimes show stunning or evenarguably perfect accuracy and fit to purpose. The validity of a model istested by measurements (when the measurements are possible and in factdone). Not everything is measured or can be measured in practical work,but a model system can provide (more or less trusted) guidance to adesigner. That model-based guidance can exist at a level of detail thatmeasurements can never provide. If the modeling applied to a design casehappens to apply well (and there are innumerable examples where modelsdo work well) this can be powerful guidance.

The present disclosure is in some ways closely similar to columnchromatography that has been put into practice millions of times, andanalyzed carefully with much checking of theory-practice correspondenceover five decades and more. With a frame of geometrical reference on theslowly or intermittently moving particle medium of the presentdisclosure, as described in the drawings, the multiple pathway Darcyflow of molten silicon around the silica particles of some embodimentscan be exactly similar to the multiple pathway Darcy flow ofconventional column chromatography or expanded bed chromatography. Thatmultiple pathway flow of molten silicon, and the dispersion of that flowmoving down an apparatus, can be modeled with an exact Reynolds numberanalog of the same apparatus geometry at room temperature with glassbeads of the same size as the formed-in-place silica spheres and withwater substituting for the molten silicon. With a steady flow of waterthrough the particle bed (for example of 0.4 molar NaCl in water) and apulsed sample (for example of 0.8 molar NaCl in water) the temporal andgeometrical dispersion of the fluid moving through the column can bemeasured in terms of peak broadening and peak asymmetry in exact analogyto standard and conventional column chromatography testing, for instanceaccording to the procedures set out in GE Healthcare Application note28-9372-07 AA; Chromatography columns—Column efficiency testing.Assuming negligible or confidently known particle conduction resistance,peak broadening and peak symmetry on this analog test implyconventionally defined HETP values, or equilibrium per unit lengthvalues substantially equivalent to HETP values, for the siliconpurification apparatus operating above 1414° C. In terms of flow ofliquid through a bed of particles the analogy of the purification of thepresent disclosure to column chromatography is close.

But in another way the purification of the present disclosure isdifferent from conventional chromatography. In conventionalchromatography, the ratio of solubility of components being analyzed andseparated between the moving medium and the stationary medium, k, ischosen to be relatively small (in the range 2 to 10). The velocity atwhich different compounds being analyzed move down the column isproportional to 1/(k+1) times the rate of carrier liquid moving down thecolumn, so that different compounds with different k's separate in a wayuseful for analysis. In conventional chromatography elements orcompounds being separated travel down the column at rates roughlybetween ½ and 1/10^(th) of the rate of the carrier liquid moving downthe column. (The carrier liquid is called the eluent). In analogy, forevery one of the 98 natural impurity elements j there is a value k_(j)for a particular selective oxidation solvent. In one embodiment of thepresent disclosure, with liquid silicon and a silica or silicatestationary (or slowly moving) solvent medium, values of k_(j) for manyelements j are decades larger than the roughly 2 to 10 size useful forchromatography. (Values of k_(j) for most or all elements j may be 10³,10 ⁵, 10⁸ or more.) In another embodiment, where solid ground silicon isthe solid stationary (or slowly moving) medium and the liquid is aselectively oxidizing molten salt, values of k_(j) are many decadessmaller than the 2 to 10 range useful for chromatography.

In one embodiment of the present disclosure, the silicon is liquid, theselective oxidizing solvent is silica or a silica glass, and the ratioof solubility of impurities between the molten silicon and the silicasolvent strongly favors the solvent, with k_(j)'s in the 100's, 1000's,millions or more for most or all of the impurity elements. The impurityelements complex with the silica solvent and the impurities then movedown the column at rates hundreds, thousands or millions of times slowerthan the rate at which the molten silicon moves, remaining in the silicasolvent as the countercurrently flowing silica solvent slowly movesupwards and is slowly removed at the top of the column. In this wayimpurities transfer from the liquid silicon into the solid or glassysilica solvent and stay there. In a column which can be validlycharacterized as having N theoretical plates, with a sufficient sourceof asymptotically pure solvent, the purification factor acting to purifythe silicon available for this column will be k_(j) ^(N). N can easilybe in the 100's or 1000's, in which case the numerical value of thepurification factor k_(j) ^(N) can easily exceed the maximum number ahand held calculator can display (9.999999×10⁹⁹). Numerically, thiscalculation (if it is valid) indicates that there's virtually no chancethat even a single atom of impurity element j remains in the purified(liquid) silicon. If the purification factor k_(j) ^(N) predicts animpurity concentration much smaller than can be detected, and muchsmaller than any thought to have a technical effect, the exact value ofk_(j) ^(N) is a matter of theory only, and a rough theory, off by alarge factor, can be operationally good enough, and indistinguishablefrom perfect for the purposes at hand.

The notion that there are N discrete theoretical plates in a packed bedor expanded bed column is based on the plate model of chromatography.The model, known to be inexact but useful, has been used for decadesbecause it describes chromatograph peak separation well. The plate modelis an approximation of more exact models that have been the subject ofthousands of experimental and statistical papers, and the approximationremains useful enough to be dominant for most purposes applied tochromatography. The plate model supposes that the chromatographic columnacts as if it contains a large number of separate layers, calledtheoretical plates. It is important to remember that the plates do notreally exist; they are a figment of the imagination that helps peoplefamiliar with discrete staged processes understand the continuousprocesses at work in the column that approximate discrete stagedprocesses in practical effect. In the plate model, the liquid moves downthe column by transfer of equilibrated mobile phase from one plate tothe next. (This plate model concept is equivalent to a tanks-in-seriesmodel reflecting the number of equilibrium stages represented by thecolumn.) It is as if separate equilibrations of the sample between thestationary and mobile phase occur in these “plates”, as if each platewas a separate well mixed tank linked to other “plates” directlyupstream and downstream in a large series of discrete mixing andtransfer steps. In chromatography columns there can be thousands ormillions of these “theoretical plates”, implicitly defined by the columnperformance. For silica solvent and most impurity elements in liquidsilicon, the equilibrium binding of (oxidized) impurities in the solventmeans that the velocity of motion of the impurities in the mobile phasefrom the relatively stationary silica is substantially zero, or lessthan the average speed at which the “stationary” phase is removed. Inthis case the calculated (not measured) purification factor k_(j) ^(N)can correspond to perfect (“asymptotic”) purification—and thepurification involved involves no energy input beyond the energy cost ofmelting the material, the small flow work of moving the silicon throughthe silica solvent, and the losses involved in preparing and expendingthe silica solvent.

Inferences about system purification based on more-or-less completeanalogies to column chromatography, and inferences based on chemical andphysical calculations based on more-or-less trusted principles, canproduce calculated results and calculated concentrations based on modelsthat can sometimes be compared to direct measurements. Multistageselective oxidation silicon purification according to the presentdisclosure involves more-or-less close analogies to chromatographypractice. The analogies are closest and seem to be most reliable for the“bubble ultrapurifier” stage where thin walled silica spheres are formedin place by bubbling oxygen through molten silicon and these spheresfloat upward in a more or less tightly packed bed (which may or may notbe expanded so that the spheres do not touch) while evenly introducedliquid silicon flows downward past these silica spheres. The “bubbleultrapurifier” involves moving particles rather than a fixed solidmedium, and is a steady-state-steady flow system rather than a batchoperating system. In the “bubble ultrapurifier” the silica wallthickness of the particles is generally less than a micron, so thatequilibration between silica glass solvent and silicon is fast. Themultipath silicon flow motion between the spheres should be exactlysimilar to that seen in column chromatography (for a moving frame ofreference centered on the spheres). The “bubble ultrapurifier”—fed witha molten silicon feedstock with a low enough initial total concentrationof impurities (perhaps less than 100 ppm atomic), with its moltensilicon feed also purified of corrosive elements such as Ca that woulddegrade its sapphire container surface, is intended to producepurifications for most or all impurity elements corresponding toconcentrations many decades below measurable concentrations. Earlierstages of purification, including a liquid silicon purifier where thesilica solvent is solid rounded grains of silica, or a solid siliconpurifier using a selectively oxidizing molten salt, will be morecomplicated to model, and will involve greater modeling uncertainties,because diffusion resistances are far higher. But these earlier stagesof purification will involve inputs and outputs where the concentrationsof impurities in the silicon are measurable for many or all impurityelements.

The mechanics of the mathematics used in modeling is continuous anddifferentiable, and in mathematics division of numbers can proceedwithout limit. But physical material is made up of discrete atoms. Toavoid modeling confusions that can otherwise occur, it is analyticallyand conceptually useful to accommodate this difference by defining thenotion of “asymptotic purity” with respect to a particular element as aconcentration of less than 1.66×10⁻²⁴, a state where the odds that asingle impurity element atom per mole occurs is less than one. This“asymptotically” low concentration is a statistical concept only, but itis a conceptually clear and in that sense practical definition ofperfect purity. Applied to a purification factor of k_(j) ^(N) and aninitial concentration, there may be uncertainties about theconcentration, uncertainties about the value of k_(j), and uncertaintiesabout the value of N. There may be uncertainties about the model. But itmay still seem clear, subject to any available evidence and subject toreasonable estimates that numerical understandings of these things aregood enough for reasoned design calculation. It may still seem clearthat the product of these factors, even including the uncertainties, isless than 1.66×10⁻²⁴ and corresponds to asymptotic purity. In thissense, it may make sense to design a purification system for asymptoticpurity with respect to most or all impurity elements. Plainly, such adesign procedure will be conservative in the sense that an impurityconcentration many orders of magnitude higher than asymptotic purity maybe perfect for any practical purpose.

Silicon purification can be done by arranging purifiers in series, withdifferent stages removing different impurities with differenteffectiveness. Different stages will be subject to differentpurification specifications. For M different purification reactors inseries, for atomic numbers i from 1 to 13 and for atomic numbers i from14-103 (all the atomic numbers except for silicon, atomic number 14) andfor a purification factor α_(ij) for each element in each reactor, wewant total impurity concentrations of each of the i elements to be lowenough, and ideally asymptotically low. We also want to minimize totalsilicon losses, and total energy and capital costs. Each purifier stagej will have a purification factor α_(ij) for each element. The designobjective of purification is to have the product

$\prod\limits_{{i = {1 - 13}}{i = {15 - 103}}{j = {1 - M}}}^{\;}{\alpha_{ij} \times {input\_ concentration}_{ij}}$

below a working target concentration (ideally asymptotic purity) at theexit of the last (M^(th)) reactor for each impurity in the PeriodicTable.

Some purification stages (for example, a molten salt stage) may addimpurities as well as remove them. The addition of these impurities maybe tolerable if the impurities added are readily removed in downstreamstages. In general, the set of designs that can meet the objective ofadequate (or even asymptotic) purification for every element of thePeriodic Table is a large, arguably infinite set. The practical designtask, for huge production scales or smaller scales, is to get thedesired silicon purification at an acceptable and reasonably small(ideally minimum) cost in a way that the designers and operatorsadequately trust and understand.

Ordinary metallurgical silicon from the smelter, prior to ladletreatments, has an impurity concentration of roughly 1%, or roughly 10⁴parts per million atomic. The task of pulling this concentration downfrom 10⁴ to 100 or 10 ppma may be called “coarse purification.” Thiscoarse purification task is qualitatively different, and involves muchmore impurity mass, than the task of pulling impurity concentrationsdown from 1 or 10 ppm to concentrations of parts per trillion or less, atask which may be called “ultrapurification”. Logically, andpractically, the same purifier stage may serve as a coarse purifier forsome elements, an ineffective purifier stage for some other elements,and an ultrapurification stage for yet other elements. To design a stagefor higher purifications for more elements typically involves addeddesign care and sophistication, which may involve some expense, but thisadded design care and sophistication may be justified in terms of totalplant cost or effectiveness, especially if enormous production volumesare involved.

For instance, ground silicon particles at temperatures near to themelting point of silicon have some impurity elements that diffuserapidly enough through the solid silicon so that a selectively oxidizingmolten salt can remove large fractions of the impurity mass of manyelements. As the flow pattern of particles and salt becomes more stableand with more orderly countercurrent character, and as the means topurify the recycled molten salt becomes more effective, a molten saltsolid purification stage of this kind may become an ultrapurifier withrespect to many elements that diffuse rapidly in crystalline silicon(including the platinum group elements) while having little purificationeffect on the low sold diffusivity impurity elements (including B and P)near silicon on the periodic table. Design choices on the development ofsuch a solid purification stage will involve the flow teaching of thisdisclosure, but may also involve design efforts not foreseen or limitedby this disclosure, which does show the effectiveness of predictable,high interfacial area, high gradient Darcy flows for the class of suchsolid phase silicon purifiers.

In another example, putting molten silicon through an expanded bed orpacked bed of silica particles that serve as both oxygen sources andsolvents for selective oxidation of impurities will work effectively asa course purifier for most impurity elements and for most of theimpurity mass in the silicon passed through the silica. This flowstructure may also serve inherently as an ultrapurifier for manyelements (including Ca, Mg, and Al). With more design sophistication,particularly with the addition of other fluxes to the silica, such a“coarse” purifier section may become a more effective purifier for moreelements. Design choices on the development of such a moltensilicon—silica solvent purification stage will also involve the flowteaching of this disclosure, but may also involve design efforts notforeseen or limited by this disclosure, which does show theeffectiveness of predictable, high interfacial area, high gradient Darcyflows for the class of such molten silicon silica particle purifiers.

FIGS. 1a, 1b, 1c, 1d, and 1e are schematic representations showing flowrelations with respect to Darcy flow important to understanding thecurrent disclosure. Chromatography involves Darcy flows where the eluentpassage length and the transit time for any particular chemical is veryuniform. The impurity sorption and complexing necessary for siliconpurification involves similar flows, with multiple equilibria closelysimilar to “heights equivalent to a theoretical plate” or “HETP,” butthe flow paths can be curved and transit times for different streamlinescan vary so long as every streamline involves a large enough number ofeffective equilibrations. The embodiments of the present disclosureinvolve Darcy flows more or less similar to the flows in columnchromatography. These flows are much more predictable and homogeneous atthe molecular scales where chemistry happens, involve much more rapidand statistically reliable mixing, and are much more useful forpurification than the open, eddying mixing flows that occur with liquidsilicon in a large scale ladle, or in a crucible, with silicon contactto a flux stirred by various bubbling, inert gas jet, electricalinduction, or other stirring contact means. Very incomplete mixing, withsurprisingly heterogeneous mixing statistics, is characteristic ofturbulent flows. The heterogeneous nature of ordinary turbulent mixing,including the mixing that occurs in prior art silicon purification, isusually invisible to us, but can be visualized clearly in special flowvisualization experiments, including many that have produced memorablephotographs. Excellent pictures for this purpose are included as FIGS.162-166 in An Album of Fluid Motion, Assembled by Milton Van Dyke.Perhaps the most vivid is the Album's FIG. 166, taken by Dimotakis, Lyeand Papantoniouu, showing mixing in a turbulent jet of dyed waterinjected into a tank of water. A laser plane illuminates the jet showingthe concentration of jet fluid in the plane of symmetry of the jet.Mixing at large scales, and yet more at the molecular scales wherechemistry happens, is strikingly incomplete, with big lumps of fluid inthe pictured jet practically unmixed. In the Annual Review of FluidMechanics, Vol. 37: 329-356 (2005) Paul Dimotakis summarizes basicproblems about turbulent mixing, which occurs across a broad spectrum ofscales, all much larger than the scale of chemical species diffusion.With enough stirring of initially unmixed liquids, interfacial areasincrease, diffusion distances decrease and concentration gradientsincrease in a turbulent flow, and eventually a stirred volume (forinstance a cup of coffee with creamer) approaches molecular scalehomogeneity. But the process of turbulent mixing is relatively slow andchaotic at the microscale where chemistry happens, and requires bothtime and work. Chemists who work to mix liquids to get completereactions, or who work to dissolve crystals in nearly saturated liquids,know from experience, and almost by reflex, how slow turbulent mixingtypically is.

For silicon purification it is important to maximize interfacial areas,maximize concentration gradients, minimize diffusion distances, andimportant to provide an orderly, statistically predictable contactbetween the silicon and the solvent. Darcy flows such as those thatoccur in groundwater aquifers, in various filtration arrangements, andin chromatography, are characterized by extremely large interfacialareas between liquid and the particles the liquid flows through. Theconcentration gradients between liquid and particles are high becausethe diffusion distances between liquid and particles are small. Beforeequilibrium is reached, the concentration gradients within the particlesare large because the particles are small. If the particles are thinwalled, equilibration can be yet faster. Orderly, statisticallypredictable contact between the silicon and the solvent can be arrangedin Darcy flows.

FIG. 1a is a sketch of Darcy flow of a liquid moving through particleswhere the liquid and particles have flow velocities. The liquid and theparticles each have a mean velocity, and can be flowing in the same oropposite directions. The sketch is useful for some simple definitions.Is the liquid and particle flow moving in the same direction(concurrent) or moving in opposite directions (countercurrent). Is oneof the media stationary? Does the flow force exerted by the liquidmoving through the particles act to compress the particles or separatethe particles? Do the flow forces on the particles reinforce or opposebuoyancy forces? Concurrent flows, countercurrent flows, flows wherebuoyancy opposes flow motion and flow motion can separate the particles,and flow fields where drag forces and buoyancy both compress theparticles can all be useful for silicon purification. Darcy's law forflow through porous media or particles is similar to Ohm's law forelectricity, and is

$Q = \frac{\kappa \; {A\left( {p_{b} - p_{a}} \right)}}{\mu \; L}$

where κ is the permeability per unit area and μ is the viscosity. FIG.1b shows a sketch corresponding to the definition, illustrating acircumstance where flow streamlines of a liquid through a particlepacked tube are straight and uniform.

FIG. 1c shows a schematic representation of a column having Ntheoretical plates dividing the column length, a tanks-in-series modelthat is conceptually useful and widely used in chromatography. Thefigure illustrates the idea of “heights equivalent to a theoreticalplate” or “HETP” which is useful and widely used in chromatography,countercurrent exchange, and elsewhere. The analogy is useful fordiscussion of what happens in a chromatography column or in the Darcyflows of the present silicon purification disclosure. FIG. 1e is similarto FIG. 1c and illustrates a length equivalent to a theoreticalequilibrium for a curved path or passage.

For chromatography it is vital that the rate of elution of a chemicalbeing separated be exactly uniform through all eluent streamlines of thecolumn, so that transit times through the column are tightly distributedand separation occurs. This spatial uniformity is not necessary forpurification, which has the objective of sorbing, complexing, andremoving all the impurities into a solvent stream rather than separatingthese impurities spatially for analysis. Curved passages without uniformstreamline lengths are acceptable for the absorption and chemicalcomplexing purification used in silica purification of silicon. For apacked bed, the length equivalent to a full equilibration between theflowing liquid and the surface of the particles (for instance, for thereversible adsorption desorption of chromatography) is typically about 3mean particle diameters for commercial chromatography packings andmaterials (GE Healthcare Application note 28-9372-07 AA; Chromatographycolumns—Column efficiency testing: “Optimal column efficiency typicallycorresponds to an experimentally determined reduced plate height of h≦3for the porous media employed in bioprocess chromatography”.) The lengthfor equilibration between liquid and particle surfaces for siliconpurification according to the present disclosure will be similar (3-5mean particle diameters) for reasonably packed flows with curved orstraight flow paths. For purification, flow path uniformity and transittime uniformity through the silica glass sorption bed is not essential.What is essential is that the number of equilibrium sorptions issufficiently large for all the streamlines through which the siliconpasses.

FIGS. 1a-1e do not illustrate all the characteristics of Darcy flow(which have been set out extensively in vector or tensor form elsewhere)but the figures do illustrate questions relevant to the siliconpurification designs of the present disclosure, questions that apply tolarge scale patterns and to smaller scale volumes of the flow. Keyquestions are:

Is the direction of the particle flow and fluid flow the same ordifferent?

Is the direction of buoyancy force and particle drag force the same ordifferent?

What path length corresponds to an “equilibrium length” or single HETPlength for the particles, composition, and packing were these particlesin a chromatography column? (This length should be in the range from 3to 10 average particle diameters.)

What is the minimum number of “equilibrium lengths” a molecule ofsilicon passes through moving through a purifier? For purification theminimum path length is much more important than the average number ofpath lengths. To economize on solvent, it is desirable for thedistribution of flow lengths (and therefore the solvent loading) to befairly uniform.

How do the flow streamlines of fluid flow and particle flow foldtogether? Is it a countercurrent flow where the highest purity isapproximately the same as the purity possible if the silicon were washedwith an infinite source of clean solvent. Or is it concurrent flow, withat most one chemical equilibrium stage possible?

How clean is the solvent source in the ways that matter forpurification? (Each impurity element counts as a separate impurity andat low impurity concentrations in the solvent these element by elementconcentrations are essentially independent.)

These simple questions, which can be easily asked and answered for aparticular flow, will clarify the function of the current disclosurepurifiers, which all utilize Darcy flows or flows closely approximatingDarcy flows, with strong diffusive coupling between liquid and solidsurfaces, with extremely large interfacial surface areas, and withrelatively short diffusion distances within the particles.

Applicant discovered that Darcy flow principles can be applied tosystems for silicon purification. The intense, fine scale observationthat skilled chemists often give to chromatography can be applied tosilicon purification employing Darcy flows, as well.

The objectives of silicon purification and chromatography, and thefunctional details involved, are similar in essential ways, anddifferent in others. The purpose of chromatography is to separate(un-mix) two or more initially mixed compounds so that these compoundsare separated in space. The separation can occur because the ratio ofaffinity of the compounds to the fixed and moving media differ, so thatthey move down the column at different rates. All compounds move downthe column at the same rate when they are actually dissolved in theeluent liquid. But molecules of different compounds spend a differentfraction of their time sorbed onto the stationary medium particles, sothe average velocity varies from compound to compound. For thisseparation to be happen sharply enough to be useful, the flow pathlengths for all the fluid elements (or tracer compounds) passing througha chromatography column have to be as tightly distributed as possible,so that all of a particular tracer (or compound being separated)injected into a column at the same time pass out of the column (or crossthe same line or the same plane) at nearly the same time. Thechromatogram is a mapping of concentration (or some measure ofconcentration) versus time.

For silicon purification, no such mapping is involved and thatchromatographic spatial detail and that more-or-less exact streamlinealignment is unnecessary. All that's needed is that each fluid elementpath includes enough equilibrations for (ideally perfect) purification.Each equilibrium strongly favors sorption in the silica or glassysolvent. The more equilibria the better the purification.

FIGS. 2a, 2b, and 2c illustrate notions of countercurrent exchange andconcurrent exchange between solvent and silicon, which are important foreffective silicon purification according to the present disclosures, andclosely correspond to and provide detail with respect to thetank-in-series “theoretical plate model” described in FIGS. 1d and 1 e.

In the concurrent silicon-silica flow modeled in FIG. 2a , liquidsilicon and silica particles flow in the same direction, and FIG. 2aillustrates 30 separate “theoretical plates” along the contact. (In thereal case being modeled, the silica and silicon equilibratecontinuously, as illustrated in FIG. 1c .) In a concurrent flow likethis, the silicon and solvent can only equilibrate once—if fullequilibration is achieved in the first “plate” no further separationoccurs on the following 29 plates. If effective equilibration is muchslower, a full chemical equilibration (which depends not only onchemistry and on diffusion between the silicon and the particlesurfaces, but also on the diffusion from the particle surfaces into theparticle) may not have occurred over the full 30 contacts. The coarsepurification in the purifier of FIG. 8 is concurrent flow like this, andfor this coarse purifier less than a full chemical equilibration betweensilicon and silica would constitute satisfactory coarse purification.

FIG. 2b shows a plate model with countercurrent silicon-solvent flow,with the silicon and the solvent flowing in opposite directions. As inthe case of FIG. 2a , there are 30 “theoretical plate” divisionsillustrated. In a countercurrent flow like this, under conditions wherediffusion is fast enough so that chemical equilibration occurs in each“plate”, there are 30 equilibrations in series. As described in moredetail in discussions of FIG. 3, this countercurrent arrangement permitsenormously more complete separation if the solvent remains well awayfrom saturation and if diffusion between the silicon and the silicasolvent is fast enough. The purification involved depends on wellordered flows that occur in Darcy flows, and that can occur in carefullydesigned packed columns for liquid-liquid extraction, but cannot occurfor the ordinary turbulent conditions characteristic of prior artsolvent based silicon purification.

FIG. 2c illustrates the idea that the notions of countercurrent exchangeand concurrent exchange make sense for curved streamlines as well asstraight streamlines.

The following relations apply to a countercurrent purificationarrangement to the extent that the flow arrangement contains (or can bewell approximated by) ideal countercurrent exchanges and the silicon hasbeen coarsely purified so that the impurity concentrations in thesolvent remain low enough so that the equilibrium silicon-solvent ratioremains constant for each impurity element. If an ideal countercurrentexchange between silicon and a solvent is arranged for a particulari^(th) element, after such a coarse purification, there is a Nernstian(constant) equilibrium separation factor α_(i) between the silicon andthe solvent. A number N of countercurrent exchanges occurs. As thesilicon flows through the countercurrent exchanges along the exchanger,the number of exchanges goes from 0 at the start to N at the exit. Thefinite increment approximation formula for purification after nexchanges is shown in Formula (1) below

y _(n,i) =y _(0,i)α_(i) ^(n)+α_(i) x _(0,i)  Formula (1)

-   -   where

$\alpha_{i} = \frac{{equilibrium}\mspace{14mu} {concentration}\mspace{14mu} {in}\mspace{14mu} {the}\mspace{14mu} {silicon}}{{equilibrium}\mspace{14mu} {concentration}\mspace{14mu} {in}\mspace{14mu} {the}\mspace{14mu} {solvent}}$

for the i^(th) element in the silicon,

-   -   y_(n,i) is concentration of the i^(th) element in the silicon        after n exchanges,    -   y_(0,i) is concentration of the i^(th) element in the silicon at        the entrance of the exchanger (at 0 exchanges),    -   x_(0,i) is concentration of the i^(th) element in the solvent        entering the exchanger, and        -   n is the number of theoretical equilibrium exchanges            counting along the exchanger from the entrance of the            silicon.

For a particular exchanger there are i such sets of equations, one foreach impurity element. The countercurrent exchange model above assumesα₁ is much less than 1; assumes that the number of theoretical exchangesin the countercurrent exchanger, N, is much greater than 1; and assumesthat the impurity concentration of the available input purificationsolvent x_(0,i) is extremely low, and ideally 0. In such a case, forsufficiently small α_(i) and sufficiently large N, the countercurrentpurification of the silicon for the ith element with a perfectly puresolvent (x_(0,i)=0) can produce asymptotic purity. However, the purityof the silicon in the exchanger, y_(n,i), can never fall belowα_(i)x_(0,i).

FIG. 3 illustrates such a countercurrent exchange for 5 stages(theoretical plates) on the assumption of perfect input solvent purity,where x_(0,i) and therefore α_(i)x_(0,i) equal zero. With an initialimpurity concentration of y_(0,i) the concentration after 5 exchanges isy_(0,i)α_(i) ⁵. For silicon and silica and most impurity elements, therelevant concentration ratio α₁ will be much less than 0.01, and α_(i)^(n) will be an extremely small number, approaching 0 in the limit as Nbecomes large. The model illustrates 5 “theoretical plates” but a realpurifier may have many 100s of theoretical plates for any streamlinepath through which the silicon passes for purification, providing muchhigher purification then the 5 plate case illustrated. Equilibriumbetween liquid flows and particle surfaces for the kinematic viscosityof molten silicon (which is similar to that of water at 20° C.) is fastenough so that a “theoretical plate” will be in the range from 3 to 5mean particle diameters. Taking that number at 5, and the particlediameter at 200 microns, a “theoretical plate” will be a millimeter, tencentimeters will be 100 “theoretical plates”. The value of α_(i) foriron in equimolar silicon and silica will be about 4×10⁻¹², and α_(i) ⁵will be less than 10⁻⁵⁷. The computed values α₁ ²⁰ or α_(i) ⁵⁰ swamp ahand calculator display, and calculated equilibria values for most otherelements are even smaller than the one for iron. Countercurrentexchange, with the high degree of flow order that occurs in Darcy flows,has the theoretical potential to produce asymptotic purification of mostimpurity elements in metallurgical silicon. (Asymptotic purificationcould never be measured, and is an unnecessarily high and probablyunattainable standard. The point is that countercurrent exchange has thepotential to produce any degree of purification needed for any impurityelement i if values of α_(i) less than 0.1 can be found.)

FIG. 4 summarizes the basic low energy silicon purification scheme ofthe present disclosure, which involves a well insulated and ideallyadiabatic process that heats solvent (silica and additives) and siliconabove the melting point of silicon (1414° C.), that contacts the siliconand solvent(s) concurrently and countercurrently with highly orderlyflows (ideally Darcy flows) above 1414° C., to remove the impuritiesfrom the silicon and transfer these impurities to the solvent, means tocollect the impurity-laden slag produced by the silicon-solvent contactabove 1414° C. and dispose of it at a lower temperature, and means tosolidify and cool the silicon. Setting heat losses aside (and systeminsulation is a major, separate challenge not treated in thisdisclosure) and assuming a source of “pure enough” silica solvent, theenergy cost of purifying the silicon would be no more than the energycost of melting the silicon and heating the silica solvent to the moltensilicon temperature. This is less than 1/50^(th) the energy cost ofcurrent silicon purification. The basic point is that for an adiabatic(no net heat transfer) system, the theoretical energy requirement topurify silicon (even to asymptotic purity) according to the pattern ofFIG. 4 is little more than the energy cost to melt the silicon and heatthe solvent. Extremely high purifications (even asymptoticpurifications) are possible because the formula for chemical equilibriumΔG_(i)=−RT ln K expresses equilibrium for a particular element i as aratio K. If equilibrium can be achieved at every stage, one stage ofequilibrium purification exchanging with a perfectly pure solventreduces the concentration by a factor of K. Transferring the purifiedmaterial from this stage, and exchanging again with a perfectly puresolvent reduces the concentration by another factor of K, for a totalpurification factor of K². Additional stages increase purification byfactors of K³ . . . K⁴ . . . K⁵ and so on. Countercurrent exchange, ofthe well-ordered sort possible with Darcy flow, produces this kind ofpurification arithmetic. A point comes where the limiting factor is thepurity of the solvent available. In the purification arrangement of FIG.5, the solvent is oxidized from the purist silicon available, thepurified silicon below the countercurrent exchange.

The basic formula for purification for any impurity element i isy_(n,i)=y_(0,i)α_(i) ^(N)+α_(i)x_(0,i) where N is the number ofequilibria. The greater the value of N for any particular fluid path,the greater (and safer) the purification will be for that path, but theexact value of N, if it is large enough, doesn't matter. It is notnecessary that each fluid path involves the same N, or involve the sametransit time.

The spatial neatness of a well packed chromatograph column may be usefulfor a silicon purification arrangement using Darcy flows—it facilitatestesting in analogy to the well established testing of chromatographypractice—but it is not functionally essential.

The present disclosure provides a device for purifying silicon. In anembodiment, the device includes a vessel having a top end, an opposingbottom end, and a sidewall extending between the opposing ends anddefining a chamber. A silicon inlet is present at the top portion of thevessel for introducing molten silicon into the chamber. A gas injectionstructure is present at a bottom portion of the vessel. The gasinjection structure has a plurality of orifices for introducing a gascomprising oxygen into the chamber. The gas is introduced in the form ofbubbles, where introduction of the gas bubbles into the molten siliconoxidizes silicon at the outside of the bubbles and produces a pluralityof in situ silica-walled gas filled beads in the chamber. The deviceincludes a countercurrent exchange section located between the siliconinlet and the gas injection structure. The countercurrent exchangesection includes (1) a controlled downward flow of the molten siliconand (2) a controlled upward flow of the beads. The countercurrent flowbetween the molten silicon and the silica-walled gas filled beadsprovides intimate high area contact between the down-flowing moltensilicon and the up-flowing beads that enables impurities present in themolten silicon to transfer into the up-flowing silica walled gas filledbeads so that the down-flowing molten silicon is purified.

In an embodiment, a device for purifying silicon 10 is provided andincludes a vessel 12 having a top end 14, an opposing bottom end 16, anda sidewall 18 extending between the opposing top and bottom ends anddefining a chamber 20 as shown in FIGS. 5, 5 a and 5 b. The vessel 12 ismade of a material that is inert, or substantially inert, to moltensilicon. Nonlimiting examples of suitable material for the vesselinclude sapphire and graphite.

The device 10 includes a silicon inlet 22 at a top portion of the vessel12 for introducing molten silicon 24 into the chamber 20. The device 10includes a gas injection structure 26 at a bottom portion of the vessel12. The gas injection structure 26 has a plurality of orifices 28 forintroducing a gas into the chamber. The gas includes oxygen. Theintroduction of the gas produces a plurality of in situ silica-walledoxygen beads 30 (hereafter “beads” 30) in the chamber 20. The device 10includes a countercurrent exchange section 32 located between thesilicon inlet 22 and the gas injection structure 26. The countercurrentexchange section 32 includes (i) a controlled downward flow of themolten silicon 24 as shown by arrow 34; and (ii) a controlled upwardflow of the beads, as shown by arrow 36.

In an embodiment, an annular member 43 extends through the chamber 20.The annular member 43 is operatively connected to the gas injectionstructure 26. The annular member 43 includes an inner conduit 43 a (FIG.6) operatively connected to a gas source (not shown). The inner conduit43 a delivers the gas to the gas injection structure 26. The gasinjection structure 26 includes a hub 44 and plurality of spokes 46extending radially from the hub as shown in FIG. 5b . Each spoke 46includes a plurality of small gas insertion tubes that inject gas intothe bubble section 38. The small gas insertion tubes constitute theorifices 28. In the bubble section 38, the rising gas from the spokes 46contacts downward flowing molten silicon 24 and a silica wall formsaround the gas to form the beads 30.

FIG. 7 shows a portion of a bead 30. Each bead 30 is hollow and containsoxygen and optionally one or more additional gasses. Nonlimitingexamples of suitable additional gasses include argon and sulfur dioxide.In an embodiment, the gas includes oxygen and from 0.01 mol % to 0.1 mol% SiO₂ and/or from 0.01 mol % to 0.1 mol % argon. Hence, the spokes caninject oxygen and optional additional gasses into the bubble section 38.Each bead 30 includes a silica wall 31 that forms as a result of theinterface between the oxygen gas and the molten silicon 24 that occursin the bubble section 38. The thickness of the silica wall 31 is from0.1 microns, or 0.2 microns, or 0.3 microns to 0.4 microns, or 0.5microns, or 0.6 microns, of 0.7 microns, or 0.8 microns, or 0.9 microns,or 1.0 micron. The beads 30 have a D50 from 25 microns, or 50 microns,or 100 microns to 200 microns, or 300 microns, or 400 microns, or 500microns.

In an embodiment, the beads 30 can oxidize and consume from 0.5 vol % to1.0 vol % of the molten silicon introduced into the device 10.

The molten silicon 24 introduced into the device 10 has an impurityconcentration that is lower than the impurity concentration formetallurgical silicon, such as a total impurity concentration of lessthan 200 ppm, or less than 100 ppm, or less than 20 ppm. If the moltensilicon 24 has too high a concentration of impurities, the moltensilicon may chemically degrade the device container or saturate thesilica walls 31 of the beads 30. In an embodiment, the molten silicon 24contains less than 10 ppm molar total impurities from alkaline earthmetals and alkali metals.

In an embodiment, the molten silicon 24 introduced into device 10 has apurity of at least 99.99%.

From the bubble section 38, the beads 30 rise and enter the lowerportion of the countercurrent exchange section 32. The countercurrentexchange section 32 has a volume and the volume includes a packed bed 40of beads 30 and interstitial molten silicon 24.

The equilibria strongly favor transfer of the impurities from the moltensilicon 24 to the silica wall 31. Equilibrium between the molten silicon24 and the silica wall 31 for the beads 30 is rapid enough so that theexchange relations within the counter-current exchange section 32represent 100-fold HETP exchanges. The thinness of the silica wall 31(0.1-1.0 microns) for beads 30 yields a large interfacial area per unitsilica volume, with short diffusion distances for equilibration in thebeads 30. Molten silicon 24 flowing downward through the countercurrentexchange section 32 is in intimate diffusional contact with the beads30, similar to a fluid passing through a packed chromatography column.However, unlike the stationary phase of a conventional chromatographycolumn, the beads 30 are not stationary. Rather, the beads 30 move, orotherwise float, upward from bubble section 38 and form a packed bed 40in the countercurrent exchange section 32. The packed bed 40 slowlyfloats upward and impurity-containing beads 30 are slowly removed at theseparation section 42 of the chamber 20.

Impurities that are present in the molten silicon 24 diffuse into, orotherwise are adsorped by, the silica wall 31 of the beads 30 as themolten silicon flows through the countercurrent exchange section 32. Thetransfer of impurities to the thin silica-wall gas filled beadstransforms the beads into “glassy” beads. Bounded by no particulartheory, it is believed the countercurrent exchange section 32 with thepacked bed 40 and interstitial molten silicon 24 therebetween forms aseparation column with 10's, or 100's, or 1,000's of height equivalenttheoretical plates (HETPs), yielding a purification factor from 10⁴ or10⁶ to 10¹⁰ or more. In this way, device 10 is capable of producingultrapure molten silicon.

In the countercurrent exchange section 32, the downward flow 34 of themolten silicon 24 is a controlled flow. The downward flow 34 iscontrolled, or otherwise determined, by adjusting the rate and theamount of molten silicon that is introduced into the top of the chamber20. The upward flow 36 of the beads 30 is a controlled flow. The upwardflow 36 is controlled, or otherwise is determined, by the amount andrate of gas injected into the bottom of the chamber 20 and the amount ofresultant beads 30 formed therefrom.

In an embodiment, the controlled downward flow 34 of the molten silicon24 moves through the counter-current exchange section 32 at a rate from0.1 millimeter (mm)/second (s), or 0.5 mm/s, or 1.0 mm/s, or 2.0 mm/s,or 3.0 mm/s, or 4.0 mm/s, or 5.0 mm/s to 6.0 mm/s, or 7.0 mm/s, or 8.0mm/s, or 9.0 to 10.0 mm/s.

In an embodiment, the controlled upward flow 36 of the beads 30 movesthrough the counter-current exchange section at a rate from 0.1millimeter (mm)/second (s), or 0.5 mm/s, or 1.0 mm/s, or 2.0 mm/s, or3.0 mm/s, or 4.0 mm/s, or 5.0 mm/s to 6.0 mm/s, or 7.0 mm/s, or 8.0mm/s, or 9.0 to 10.0 mm/second.

In an embodiment, the countercurrent exchange section 32 exhibits a“steady-state/steady-flow” condition whereby (i) the net rate at whichbeads 30 are supplied at the lower end of the countercurrent exchangesection 32 and form the packed bed 40 is the same as, or substantiallythe same as, (ii) the net rate at which beads 30 are removed from theupper end of the countercurrent exchange section 32 by way of theseparation section 42. In this sense, “steady-state/steady-flow” at thetop of the chamber is steady or uniform, or substantially steady. Inother words, “stead-state/stead-flow” is achieved in the countercurrentexchange section 32 because as the packed bed 40 floats upward, themolten silicon 24 is evenly supplied at the top of the chamber 20 andflows evenly downward in a Darcy flow through the packed bed 40 (similarto the flow that occurs in conventional column chromatography). The (i)evenness and uniformity of packed bed formation at the lower end of thecountercurrent exchange section 32, in conjunction with (ii) theevenness and uniformity of the introduction of molten silicon 24 at thetop of the chamber 20, along with (iii) the evenness and uniformity ofthe removal of the beads 30 at the separation section 42 the top of thecountercurrent exchange section 32 produces the steady-state/steady-flowcondition. The steady-state/steady-flow condition ensures that themolten silicon passing through the bed 40 travels through a large numberof equilibrium contacts.

In an embodiment, the rate for the downward flow 34 is the same as, orsubstantially the same as, the rate of the upward flow 36.

In an embodiment, the countercurrent exchange section 32 includes from25 vol %, or 30 vol % to 40 vol %, or 50 vol % molten silicon 24 andfrom 75 vol %, or 70 vol % to 60 vol %, or 50 vol % beads 30.

In an embodiment, the counter-current exchange section 32 has a “plateheight” of 3 diameters, and the beads 30 have about 28 HETP's. The beads30 have a D50 from 100 microns, or 200 microns, or 300 microns, or 400microns, or 500 microns to 600 microns, or 700 microns, or 800 microns,or 900 microns, or 1000 microns yielding a counter-current exchangesection 32 having from 300, or 400, or 500, or 600 to 700, or 800, or900, or 1000 theoretical plates.

In an embodiment, the countercurrent exchange section 32 has from 300,or 400, or 500 to 600, or 700, or 800, or 900, or 1000 HETPs.

FIG. 6 shows a sectional view of the vessel 12 just below the siliconinlet 22. In an embodiment, the silicon inlet 22 includes a plurality ofsilicon injection tubes 48 (or “SITs 48”) uniformly spaced-apart asshown in FIGS. 5, 5 a, and 6. The SITs 48 extend through the separationsection 42 such that the outlet for each SIT 48 is located at the upperportion of the countercurrent exchange section 32 for the uniformintroduction of molten silicon 24 into the countercurrent exchangesection 32. Each SIT 48 includes a plurality of silicon injection holes50 extending radially from the center of each SIT 48. Although FIG. 6shows each SIT 48 having six silicon injection holes 50 (for a total of396 silicon injection holes), it is understood each SIT 48 may have 2,or 3, or 4, or 5 to 6, or 7, or 8, or 9, or 10, or more siliconinjection holes 50. Introduction of the molten silicon 24 through theSITs 48 uniformly fills the interstitial volume between the individualbeads 30 of the packed bed 40. The molten silicon 24 flows downwardevenly as the beads 30 of the packed bed 40 flow upwardly, the opposingflows thereby providing “countercurrent flow” in the countercurrentexchange section 32. By the time that the downward-flowing moltensilicon 24 has moved several times the distance between the injectiontubes, the downward flow of silicon through the packed or buoyancyexpanded silica bed is uniform, or substantially uniform, producing acounter-current Darcy flow geometry similar to that of columnchromatography.

FIG. 6 shows an embodiment wherein a plurality of spaced-apart ports 52and a plurality of spaced-apart extraction ducts 54 are present in theseparation section 42. The ports 52 introduce a media gas into theseparation section 42. The media gas imparts a positive pressure to holdor otherwise, maintain the packed bed 40 of beads within thecountercurrent exchange section 32. The media gas promotes separation ofthe beads 30 from the molten silicon 24. The introduction of the mediagas provides a balancing pressure, which in turn, provides an interfacebetween the separation section 42 with the upper surface of the packedbed 40. In the separation section 42 and above the top surface of thepacked bed 40, the interstitial volume between the beads 30 is the mediagas. Below the interface, the interstitial volume is filled with moltensilicon 24. The media gas is a noble gas (such as argon, for example) ora relatively unreactive gas such as nitrogen, and may optionally includesome hydrogen and/or steam to soften the silica bead walls.

The beads 30 form a foam when they enter the separation section 42. Thedevice 10 includes extraction ducts 54 to remove the impurity-containing(“glassy”) beads as the beads rise to the top of the counter-currentexchange section 32 and form the foam in the separation section 42.Removal occurs by way of negative pressure or suction. The media gaswith hydrogen and/or steam advantageously softens the silica walls ofthe beads 30 promoting efficient removal of the glassy beads through theducts 54 via suction or vacuum.

The vessel 12 includes a well 56. The well 56 is located below the gasinlet structure 26. The well 56 collects the molten silicon that haspassed through the counter-current exchange section 32. The moltensilicon 24 collected in the well 56 is purified molten silicon. In anembodiment, most of the impurity elements in the purified silicon willbe at such low concentrations as to be undetectable, or less than onepart per trillion.

In an embodiment, the well 56 is in fluid communication with adeoxidation column. The purified silicon is delivered to the deoxidationcolumm to remove oxygen therefrom. A nonlimiting example of a suitabledeoxidation column is an argon bubbler as shown and described in FIG.13.

FIG. 8 shows another device for purifying silicon. In an embodiment,FIG. 8 illustrates a “coarse” purifier 80 that can produce less than 1full equilibration contact between metallurgical (or “less pure”)silicon and a silica flow, but that has large contact times so thatimpurity pickup per unit solvent can be maximized. It is useful for thesilica solvent to have approximately spherical grains for even flow.Fracking sand, which is fairly pure silica with round particles, is welladapted to flow and not prone to clumping. A slurry 82 of silica andmolten silicon (perhaps with some additional additives, for example asulfate) is introduced at the top of the concurrent buoyancy stabilizedcolumn 84. The particles in the slurry separate and settle upward in thecolumn, similar to the steps involved in packing a chromatography columnwith particle-solvent slurries. Flow streamlines in column 84 are notuniform, as they would have to be in chromatography, or in the device(i.e., ultrapurifier) of FIG. 5, but any flow path for the moltensilicon passes through many (hundreds or thousands) of equilibriumlengths. Unless the molten silicon flow is rapid enough to generate dragforces that overcome buoyancy and separate the particles, the packing ofthe liquid and the particles will be roughly 3-4 volumes of silicaparticles per volume of liquid silicon.

In an embodiment, the volume ratio of liquid (molten silicon) particles(fracking sand) in the slurry is from 5:1 or 7:1 to 10:1. If flow doesnot separate the silica particles, this means that the residence time ofthe particles in the column 84 will be in the rough range from 15 timesto 40 times the residence time of the liquid silicon. For a purifierwhere the liquid does not act to separate the particles and the liquidresidence time in the column 84 is 5 minutes, the residence time of thesilica may be 75 minutes, or 100 minutes to 150 minutes, or 200 minutes.During this long time the silica particles will sorb and complex withthe impurities in the silicon flowing around them, and will become aglass, with the glass impurity concentration an increasing function ofsphere radius, and with diffusion tending to equalize the impurityconcentration through the particle. For a 10% silica flow and 1% molarimpurities in the silicon, the particles will become glass with 10%average molar concentration of impurities, with the impuritiesaccumulating roughly linearly with particle residence time. The densityof the silica-glass particles will remain lower than the density of themolten silicon, and the impurity-laden glassy particles will separate bydifferential density from the bottom of the column. The slag can betreated with an additional solvent (for example CaO) to reduce slagviscosity for convenient slag disposal.

The “coarse purifier” 80 of FIG. 8 will remove all, or substantiallyall, of the impurity elements having an energy of oxidation higher thanthat of silicon. The “coarse purifier” 80 should effectively remove mostother impurity elements, removing well in excess of 99% of totalimpurity mass from the silicon.

The addition of additives to the silica introduced at inlet 86 of FIG. 8may be useful to keep silica particles from adhering to each other, andimmobilize impurities such as gold, silver, and the platinum metalswhich complex efficiently with sulfur compounds, and/or to increase thediffusivity of the glass. Addition of one, some or all of the followingCaSO₄, Na₂SO₄, Na₂O, NaCl, and/or H₂O to the slurry may serve thesepurposes.

FIG. 9 shows another device for purifying silicon. In an embodiment,FIG. 9 illustrates a countercurrent exchanger 90 to further purifymolten silicon. The countercurrent exchanger includes concentriccolumns, or generally concentric columns, inner column 92 and outercolumn 94. A slurry 96 of relatively pure silica completely wet with thepure molten silicon is introduced into the bottom of inner column 92passage. In an embodiment, the molten silicon is the purist moltensilicon available. Structure and/or components are provided to minimizethe liquid silicon contact of the slurry, with density sortingcomponents to remove excess liquid silicon for injection upstream forfurther purification. Less pure molten silicon is introduced betweenconcentric columns 92, 94 (FIG. 9A) by way of input tube 98 and flowsuniformly into the silica to equalize pressures and pressure gradients.One or more suction tubes 100 are provided to continuously, orperiodically, remove spent silica from the countercurrent exchanger 90.The path lengths of silicon through the countercurrent exchange of FIG.9 are not uniform as they would be in chromatography, but all these pathlengths are long enough for many (hundreds or thousands) of equilibriumlengths, so that sorption of impurities into the particles is complete,or substantially complete.

In an embodiment, the exchanger 90 also includes an output tube (FIG.9A) to remove purified silicon from the bottom of the inner column.

In an embodiment, the mass flow of molten silicon to silica in theslurry introduced into the top of the inner column is greater than 9:1.

In an embodiment, the spent silica is reused as silica in the coarsepurifier 80.

Several stages of the purifier arrangement of FIG. 9 can be put inseries. They can use different purities of silica; they can usedifferent additives to the silica; and they can be constructed ofdifferent materials (for example graphite or sapphire coated alumina).

The present disclosure provides another device. In an embodiment, adevice for purifying silicon is provided and includes a vessel having atop end, an opposing bottom end, and a plurality of concentric columns.The columns are in fluid communication with each other. The deviceincludes a central column having a silicon inlet at a top portion of afirst column for introducing molten silicon into a bed of a plurality ofsilica particles to form a slurry. The device includes a first channelin fluid communication with a bottom portion of the central column forreceiving a portion of the slurry. The glassy silica particles, whichare less dense than the liquid silicon, separate from the molten siliconby differential density and rise into the first channel. Thisimpurity-laden glassy slag collects at the top of this first channel andis continuously, or intermittently, removed. The device includes asecond channel in fluid connection with the first channel which collectsthe more dense molten silicon, separated from the impurity-laden glassyparticles by differential density.

In an embodiment, FIG. 10 shows a device 110. Device 110 includes avessel 112 having a top end 114, and an opposing bottom end 116. Aconcurrent and countercurrent exchange arrangement is built in acombined form in the vessel 112. Within a first central column 118 is abed of silica particles (plurality of silica particles). In anembodiment, the silica particles are fracking sand. The central column118 receives molten silicon at inlet 120 to form a slurry 122 of themolten silicon and the silica particles. A downward flow of the slurry122 in a first central column 118 (coarse purifier) removes most of theimpurities as glassy slag 124. The glassy slag 124 is removed bydifferential density separation at slag outlet 126. Molten siliconseparated by differential density from slurry 122 flows through acountercurrent flow arrangement 128 of a first channel 130 and a secondchannel 132. The first channel 130 and the second channel 132 are influid communication with each other. A portion of the silicon 123 flowsupward in the first channel 130. The flow of silicon 123 then turns andenters the second channel 132 and flows downward. The upward flow in thefirst channel 130 and the downward flow in the second channel 132produces the countercurrent flow arrangement 128.

Structure and/or components are provided to introduce a slurry of silicaand the silicon at inlet 134. In an embodiment, the silicon is thepurist available silicon. Structure and/or components are provided toremove spent countercurrent silica at outlet 136 and form a manyequilibrium (or partial equilibrium) countercurrent exchange. The slurryof spent silica removed from the countercurrent flow arrangement 128 canbe separated, with the silica particles recycled back into the firstcolumn 118 (coarse purifier). The molten silicon entrained with thespent silica can be reintroduced upstream of the countercurrent flowarrangement 128 for further purification. Purified molten silicon iscollected at product outlet 138.

The present disclosure provides another device. In an embodiment, FIG.11 shows a device 210. Device 210 illustrates another Darcy flowbuoyancy stabilized countercurrent exchange for silicon purification—inthis case with a selectively oxidizing molten salt purifying theelements in ground solid silicon that form silicides that melt below themelting point of silicon and that removes impurities (impuritiesincluding the transition metals including Au, Ag, and the platinum groupmetals, and combinations thereof) that diffuse relatively rapidlythrough silicon crystals so that they can be selectively oxidized andremoved from the silicon particle surfaces by the selectively oxidizingmolten salt by a many theoretical exchange countercurrent flow.

In an embodiment, the device 210 includes a vessel 212 having a top end214 and a bottom end 216. A sidewall 218 extends between the opposingends 214, 216 and defines a chamber 220. A silicon inlet 222 is locatedat a top portion of the vessel 212 for introducing silicon particlesinto the chamber 220.

When the silicon particles contact the molten salt, the temperature ofthe silicon particles quickly rises and the silicon particles then havea temperature greater than 1350° C.

The device 210 includes an injection structure 224 at a bottom portionof the vessel 212. The injection structure 224 has at least one orificefor introducing a molten salt composition into the chamber 220. Themolten salt composition has a temperature greater than 1350° C. Themolten sat composition includes an oxidizer dissolved in the moltensalt. The vessel includes a countercurrent exchange section 226 locatedbetween the silicon inlet and the injection structure. Thecountercurrent exchange section 226 includes a controlled downward flow228 of the silicon particles. The countercurrent exchange section 226also includes a controlled upward flow 230 of the molten saltcomposition. The downward flow 228 and the upward flow 230 form acountercurrent flow between the silicon particles and the molten salt inthe countercurrent exchange section 226. At a bottom portion of thevessel 212, a well 232 collects purified silicon particles.

In an embodiment, the oxidizer in the molten salt composition is sulfur,or excess sulfur.

In an embodiment, the silicon particles present in the countercurrentexchange section 226 have temperature greater than 1350° C., or 1360°C., or 1370° C., or 1380° C., or 1390° C. to 1400° C.

In an embodiment, the countercurrent exchange causes impurities in thesilicon particles to diffuse to the silicon particle surface. Theoxidizer oxidizes the surface impurities and the oxidized impurities aredissolved in the molten salt.

In an embodiment, the molten salt contains the dissolved oxidizedimpurities and moves upwardly past the purified silicon particles.

In an embodiment, purified silicon particles move downwardly through themolten salt composition to the bottom of the vessel. The purifiedsilicon particles are collected in the well 232.

In an embodiment, the controlled downward flow 228 has a rate from 0.1mm/second, or 1.0 mm/second, or 2.0 mm/second, or 3.0 mm/second to 4.0mm/second, or 5.0 mm/second.

In an embodiment, upward flow 230 has a rate from 0.1 mm/second, or 1.0mm/second, or 2.0 mm/second, or 3.0 mm/second, or 4.0 mm/second, or 5.0mm/second, or 10.0 mm/second to 15.0 mm/second, or 20.0 mm/second.

In an embodiment, the rate for the downward flow 228 and the upward flow230 is the same, or substantially the same.

In an embodiment, the molten salt composition includes a molten saltselected from molten NaCl, molten KCl, molten Al₂S₃, molten Na₂S, moltenK₂S, and combinations thereof.

In an embodiment, the oxidizer is a sulfur-based composition selectedfrom the group consisting of sulfates, sulfides, and combinationsthereof.

In an embodiment, the device 210 includes a pump device in operativecommunication with the vessel 212 for moving the molten salt compositionupwardly through the vessel.

In an embodiment, the device 210 includes a melting device in fluidcommunication with the bottom end of the vessel. The melting devicereceives the purified silicon particles from the vessel 212. The meltingdevice melts the purified silicon particles to form purified moltensilicon.

In an embodiment, the vessel 212 is composed from a material selectedfrom sapphire or graphite. In a further embodiment, the vessel 212 iscomposed of graphite.

FIG. 12 shows another device for purifying silicon. In an embodiment,FIG. 12 shows a liquid-liquid countercurrent exchange through a packedsapphire bead column with molten silicon as the sapphire nonwettingliquid and a molten salt as the sapphire wetting liquid. The molten saltis a mixture of molten NaCl, molten Na₂S, molten Al₂S₃ or other saltsincluding enough excess sulfur for a significant partial pressure ofsulfur, pS, and enough silicon sulfide partial pressure to inhibit anynet silicon oxidation. The high pS molten salt selectively oxidizes anddissolves noble metals from the silicon in an isothermal many HETPexchange. The molten salt is recirculated through nearly isothermalelectrolytic plates that remove the noble metals from the molten salt sothat the recirculated clean solvent supplied to the countercurrentexchange is extremely pure with respect to the noble metals. Scaling thedrawing and assuming that one HETP is about four bead diameters in thisexchanger, the column shown would be about 10 HETPs. The liquid-liquidcountercurrent exchanger of FIG. 12 is not strictly a Darcy flow, thoughit is a close flow analogy to Darcy flow, with the solid sapphiresurfaces organizing the liquid-liquid contact of the exchanger. Themolten salt wets the sapphire surface strongly, and is immiscible withthe molten silicon, so that the salt flows upward by differentialdensity, with the absorbed film from one particle feeding another. Thesilicon flows downward through a tortuous path very similar to the paththat liquid moving through an ordinary packed bed would follow. It isunderstood that with liquid-liquid exchangers (such as the exchangershown in FIG. 12), flooding of the exchanger is to be avoided.

In an embodiment, the exchanger of FIG. 12 operates downstream of thecoarse purifier, and removes rare and noble metals (Ag, Au, and theplatinum group) and other metals that react more strongly with sulfurthan with oxygen. The exchanger of FIG. 12 effectively removes noblemetals that are difficult to remove from liquid silicon, and may addother impurities. The impurity atoms added (Na, K, Cl, S) all have veryhigh coefficients of separation in silica and silica glasses, and can becompletely removed by a downstream exchanger, for example theultrapurifier of FIG. 5.

FIG. 13 shows another device for purifying silicon. In an embodiment,FIG. 13 shows a deoxidation column 310. Molten silicon is introducedinto the column 310. An isothermal argon bubbling arrangement with argonrecirculation for removing oxygen (and any trace of sulfur) that is notremoved by the selective oxidation purification stages from the moltensilicon. Argon and the other inert gases are insoluble in pure moltensilicon. Argon bubbles will absorb oxygen (as SiO) and any sulfur (asSiS or SiS₂) as they rise through the molten silicon. Compared to themelting energy of the silicon, the mechanical energy of pumping largequantities of inert gas bubbles through the silicon is small. Siliconoxides or sulfides, and any other volatiles, including about 0.6 ppm ofsilicon vapor will be carried up with the argon. The argon that haspassed through the silicon can be readily purified by passing it througha high interfacial area covered with very reducing glass at itssurfaces. A vertical bubbling column is shown with bubble flow upward,silicon flow downward, and with the sapphire tube wall containing thebubbling interrupted with wall recirculation zones so that the siliconflow roughly approximates a countercurrent flow, without the formationof short-circuiting full vertical scale recirculation at the walls. Morethan 10 HETPs are possible with such a bubbling column, and if greaterpurification is required, similar columns can be placed in series. Theideal oxygen concentration in the silicon output may not be zero,because a small concentration of oxygen can add mechanical strength tocrystalline silicon.

In an embodiment, rising argon bubbles pass through downwardly movingmolten silicon by way of countercurrent exchange.

In an embodiment, argon bubbles pass through the molten silicon by wayof turbulent flow.

In an embodiment, the column 310 is composed of sapphire (crystallineAl₂O₃) which is insoluble in pure molten silicon.

In an embodiment, the purified silicon from device 10 is introduced intothe deoxidation column 310.

In an embodiment, the purified silicon from the device 110 is introducedinto the deoxidation column 310.

In an embodiment, the purified silicon from the device 210 is introducedinto the deoxidation column 310.

FIGS. 14 to 20 are a series of schematic diagrams of purifier componentsarranged in series for effective purification, each carrying out thebasic low energy silicon purification scheme of the present disclosure.

FIG. 14 shows the simplest ultrapurifier arrangement, a melter ofrelatively pure silicon input, the thin walled silica sphereultrapurifier, followed by argon deoxidation.

FIG. 15 shows a melter feeding molten silicon to a coarse purifier whichfeeds molten silicon to a thin walled silica sphere ultrapurifier,followed by argon deoxidation.

FIG. 16 shows a melter feeding molten silicon to a coarse purifier whichfeeds molten silicon to a countercurrent exchanger similar to that ofFIG. 9 which feeds a thin walled sphere ultrapurifier, followed by argondeoxidation.

FIG. 17 shows a melter feeding molten silicon to a coarse purifier whichfeeds two countercurrent exchangers similar to that of FIG. 9 arrangedin series, followed by argon deoxidation.

FIG. 18 shows a melter feeding molten silicon to a coarse purifierfollowed by a countercurrent molten salt exchange purification stagefeeding silicon to a thin walled silica sphere ultrapurifier, followedby deoxidation.

FIG. 19 shows a solid ground silicon purifier followed by a melter whichthen feeds the molten silicon to a thin walled silica sphereultrapurifier, followed by deoxidation.

FIG. 20 shows a solid ground silicon purifier followed by a melter whichthen feeds the molten silicon to a countercurrent exchanger similar tothat of FIG. 9, followed by deoxidation.

It is specifically intended that the present disclosure not be limitedto the embodiments and illustrations contained herein, but includemodified forms of those embodiments including portions of theembodiments and combinations of elements of different embodiments ascome within the scope of the following claims.

1. A device for purifying silicon comprising: a vessel having a top end,an opposing bottom end, and a sidewall extending between the opposingends and defining a chamber; a silicon inlet at a top portion of thevessel for introducing molten silicon into the chamber; a gas injectionstructure at a bottom portion of the vessel, the gas injection structurehaving a plurality of orifices for introducing a gas comprising oxygeninto the chamber in the form of bubbles, where introduction of the gasbubbles into the molten silicon oxidizes silicon at the outside of thebubbles and produces a plurality of in situ silica-walled gas filledbeads in the chamber; a countercurrent exchange section located betweenthe silicon inlet and the gas injection structure, the countercurrentexchange section comprising (1) a controlled downward flow of the moltensilicon; (2) a controlled upward flow of the beads; wherein thecountercurrent flow between the molten silicon and the silica-walled gasfilled beads provides intimate high area contact between thedown-flowing molten silicon and the up-flowing beads that enablesimpurities present in the molten silicon to transfer into the up-flowingsilica walled gas filled beads so that the down-flowing molten siliconis purified.
 2. The device of claim 1 wherein the transfer of impuritiesto the silica-walled gas filled beads convert the relatively pure beadsilica walls initially formed by bubbling to less pure bead silicawalls, so that the plurality of up-flowing gas filled beads carryimpurities upward as the molten silicon flows downward.
 3. The device ofclaim 1 wherein the countercurrent exchange section has a volume and thevolume comprises a packed bed the of beads and interstitial moltensilicon.
 4. The device of claim 1 wherein the countercurrent exchangesection comprises from 20 vol % to 35 vol % molten silicon and from 80vol % to 65 vol % silica-walled oxygen beads.
 5. The device of claim 1wherein the bead silica walls have a thickness from 0.1 microns to 1.0micron.
 6. The device of any of claim 1 wherein the silicon inletcomprises a plurality of spaced-apart injection tubes.
 7. The device ofclaim 1 wherein the gas injection structure comprises a hub and aplurality of spokes extending radially from the hub, each spokeincluding a plurality of gas orifices.
 8. The device of claim 1 whereinthe impurity elements in the purified silicon output will be at such alow concentration that they are undetectable, or less than one part pertrillion.
 9. The device of claim 1 wherein the vessel comprises aseparation section located above the silicon inlet and thecountercurrent exchange section, and the upwardly moving beads in theseparation section form a foam.
 10. The device of claim 9 comprising anextraction member in operative communication with the separationsection, and the extraction member removes the foam from the chamber.11. The device of claim 1 comprising a well for collecting the purifiedmolten silicon, the well located below the gas inlet.
 12. A devicecomprising a deoxidation column in fluid communication with the well ofclaim
 11. 13. The device of claim 1 wherein the beads have a D50 from100 microns to 500 microns.
 14. The device of claim 1 wherein the gascomprises oxygen and SO₂.
 15. The device of claim 1 wherein the gascomprises oxygen and argon.
 16. The device of claim 1 wherein the moltensilicon introduced into the chamber has a purity of at least 99.99%. 17.The device of claim 1 wherein the controlled downward flow of the moltensilicon moves through the counter-current exchange section at a ratefrom 0.1 millimeter (mm)/second (s) to 10.0 mm/s.
 18. The device ofclaim 1 wherein the controlled upward flow of the beads moves throughthe counter-current exchange section at a rate from 0.1 mm/s to 10.0mm/s.
 19. The device of claim 1 wherein the countercurrent exchangesection exhibits a steady-state/steady-flow whereby the net rate atwhich the beads are supplied at a lower end of the countercurrentexchange section is substantially the same as the net rate at which thebeads are removed from an upper end of the countercurrent exchangesection.
 20. The device of claim 9 wherein the separation sectioncomprises a plurality of spaced-apart ports for introducing a media gasinto the separation section.